JPH04248811A - Suspension polymerization of vinyl chloride - Google Patents
Suspension polymerization of vinyl chlorideInfo
- Publication number
- JPH04248811A JPH04248811A JP2370091A JP2370091A JPH04248811A JP H04248811 A JPH04248811 A JP H04248811A JP 2370091 A JP2370091 A JP 2370091A JP 2370091 A JP2370091 A JP 2370091A JP H04248811 A JPH04248811 A JP H04248811A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- vinyl chloride
- weight
- autoclave
- deionized water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000010557 suspension polymerization reaction Methods 0.000 title description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- 239000003112 inhibitor Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000000375 suspending agent Substances 0.000 claims abstract description 14
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000010558 suspension polymerization method Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 19
- 239000002245 particle Substances 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 abstract description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract 2
- 230000000379 polymerizing effect Effects 0.000 abstract 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 1
- 239000011976 maleic acid Substances 0.000 abstract 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 17
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- 238000002156 mixing Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- -1 pH regulators Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- VGZZAZYCLRYTNQ-UHFFFAOYSA-N 2-ethoxyethoxycarbonyloxy 2-ethoxyethyl carbonate Chemical compound CCOCCOC(=O)OOC(=O)OCCOCC VGZZAZYCLRYTNQ-UHFFFAOYSA-N 0.000 description 1
- UYQYTUYNNYZATF-UHFFFAOYSA-N 6-methyl-4,6-bis(octylsulfanylmethyl)cyclohexa-1,3-dien-1-ol Chemical compound CCCCCCCCSCC1=CC=C(O)C(C)(CSCCCCCCCC)C1 UYQYTUYNNYZATF-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- UUPWEGAONCOIFJ-UHFFFAOYSA-N CCCCC(CC)COC(=O)OOC(O)=O Chemical compound CCCCC(CC)COC(=O)OOC(O)=O UUPWEGAONCOIFJ-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- DDMBAIHCDCYZAG-UHFFFAOYSA-N butyl 7,7-dimethyloctaneperoxoate Chemical compound CCCCOOC(=O)CCCCCC(C)(C)C DDMBAIHCDCYZAG-UHFFFAOYSA-N 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- GLOQRSIADGSLRX-UHFFFAOYSA-N decyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCCCC)OC1=CC=CC=C1 GLOQRSIADGSLRX-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 230000035936 sexual power Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- KGKNBDYZZIBZQL-UHFFFAOYSA-N tert-butyl carboxyoxy carbonate Chemical compound CC(C)(C)OC(=O)OOC(O)=O KGKNBDYZZIBZQL-UHFFFAOYSA-N 0.000 description 1
- 238000001248 thermal gelation Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は塩化ビニル又は塩化ビニ
ルを主成分とするこれと共重合可能なモノマー混合物（
以下塩化ビニルと称す。）の懸濁重合法において、重合
開始剤の仕込み時間、及び昇温時間を短縮して重合工程
の生産性を向上させ、合わせてフィシュアイ、粒度分布
の改善及びスケール付着防止をはかる懸濁重合法に関す
るものである。[Industrial Application Field] The present invention relates to vinyl chloride or a monomer mixture copolymerizable with vinyl chloride, which has vinyl chloride as its main component (
Hereinafter referred to as vinyl chloride. ) suspension polymerization method, which improves the productivity of the polymerization process by shortening the polymerization initiator charging time and temperature raising time, and also improves fisheye and particle size distribution and prevents scale adhesion. It's about legality.
【０００２】0002
【従来の技術】通常塩化ビニルの懸濁重合はバッチ式で
行われ、オートクレーブに脱イオン水、懸濁剤、重合開
始剤及び添加剤を仕込んだ後、系内を脱気して塩化ビニ
ル等を仕込み、攪拌しながらオートクレーブのジャケッ
トに温水循環又は水蒸気を通し、重合温度まで昇温して
重合反応を開始させる。その後、重合反応熱が出てきた
時点からオートクレーブのジャケットに冷却水を通して
重合温度を一定に保つべく冷却を行い、所定の重合率に
なるまで反応を継続し、次に塩化ビニル等のモノマーガ
スを回収して重合体をオートクレーブから排出する一連
の重合操作を行っている。[Prior Art] Suspension polymerization of vinyl chloride is usually carried out in a batch process, in which deionized water, a suspending agent, a polymerization initiator, and additives are charged into an autoclave, and then the system is degassed to produce vinyl chloride, etc. is charged, hot water is circulated or steam is passed through the jacket of the autoclave while stirring, and the temperature is raised to the polymerization temperature to initiate the polymerization reaction. After that, cooling water is passed through the jacket of the autoclave to keep the polymerization temperature constant from the moment the heat of the polymerization reaction is generated.The reaction is continued until a predetermined polymerization rate is reached, and then monomer gas such as vinyl chloride is added. A series of polymerization operations are performed in which the polymer is recovered and discharged from the autoclave.
【０００３】0003
【発明が解決しようとする課題】しかし、以上のような
従来法では昇温時間に要する時間が生産性低下の一因と
なっている。かかる問題を解決するため、種々の方法が
考えられている。However, in the conventional methods as described above, the time required for heating up the temperature is one of the causes of reduced productivity. Various methods have been considered to solve this problem.
【０００４】特開昭５７−５７０４にあるような重合温
度又はそれ以上に加温した水、懸濁、剤、塩化ビニル等
と重合開始剤を一括してオートクレーブに仕込み、ただ
ちに重合反応を開始させる方法があるが、この方法は重
合温度付近で塩化ビニル、水、懸濁剤が接触する事にな
るため、粒度が不安定となり、特に粗粒の製品が多くな
る。又フィシュアイも著しく多くなるという品質上の欠
点を有し、得策でない。 或るいは特開昭６０−４７
００７にあるようなオートクレーブに懸濁剤、重合開始
剤、その他添加剤及び塩化ビニルを仕込み、次いで重合
温度またはそれ以上に加温された水を仕込む方法が有る
が、この方法は重合缶内壁にスケールが生成し、また温
水の仕込み初期における重合の均一化が難しく、粗粒が
生成し、フィシュアイの良くない製品となる。[0004] Water, suspension, agent, vinyl chloride, etc. heated to the polymerization temperature or higher as described in JP-A No. 57-5704, and a polymerization initiator are charged all at once into an autoclave, and the polymerization reaction is immediately started. There is a method, but in this method, the vinyl chloride, water, and suspending agent come into contact near the polymerization temperature, resulting in unstable particle size and a particularly large number of coarse-grained products. In addition, it has a quality defect in that the number of fisheyes increases significantly, which is not a good idea. Or JP-A-60-47
There is a method of charging a suspending agent, a polymerization initiator, other additives, and vinyl chloride into an autoclave as shown in 007, and then charging water that has been heated to the polymerization temperature or higher, but this method does not cause damage to the inner wall of the polymerization vessel. Scale is formed, and it is difficult to homogenize the polymerization at the initial stage of charging hot water, resulting in coarse particles, resulting in a product with poor fish eye quality.
【０００５】又特開昭５４−４７７８５にあるような３
０℃以下の水、懸濁剤と重合開始剤をオートクレーブに
仕込み、その後塩化ビニルを仕込み、攪拌混合した後加
熱した水を仕込んで重合を開始する方法においては、重
合缶内壁にかなりスケールが発生する欠点があり実用上
の問題を有する。[0005] Also, 3 as described in Japanese Patent Application Laid-Open No. 54-47785
In the method of charging water below 0℃, a suspending agent, and a polymerization initiator into an autoclave, then charging vinyl chloride, stirring and mixing, and then charging heated water to start polymerization, a considerable amount of scale occurs on the inner wall of the polymerization can. This has the disadvantage of causing practical problems.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、この欠点
を解決し、重合工程のサイクル時間を短縮すべく鋭意検
討を進めた結果、攪拌の開始時期、重合禁止剤の使用方
法及び重合開始剤の仕込方法を工夫することによって上
記の欠点を解決し、本発明にいたった。[Means for Solving the Problems] As a result of intensive studies to solve this drawback and shorten the cycle time of the polymerization process, the present inventors have discovered the timing of starting stirring, the method of using a polymerization inhibitor, and the The above drawbacks were solved by devising a method for charging the initiator, leading to the present invention.
【０００７】すなわち、本発明は塩化ビニルの懸濁重合
においてまずオートクレーブ中に重合系の全水量のうち
、２０〜５０重量％の常温の脱イオン水、懸濁剤、重合
禁止剤を仕込み、攪拌を開始した後、塩化ビニルと重合
系の全水量の５０〜８０重量％を重合温度以上に加温さ
れた脱イオン水とを仕込むことによって重合系内を反応
温度まで昇温させ、続いて重合開始剤を仕込んで重合す
ることを特徴とする塩化ビニルの懸濁重合法を提供する
ものである。That is, in the suspension polymerization of vinyl chloride, the present invention first charges deionized water at room temperature, a suspending agent, and a polymerization inhibitor in an amount of 20 to 50% by weight of the total amount of water in the polymerization system into an autoclave, and then stirs the mixture. After starting the reaction, the temperature inside the polymerization system is raised to the reaction temperature by charging vinyl chloride and 50 to 80% by weight of the total amount of water in the polymerization system with deionized water heated above the polymerization temperature, and then the polymerization is started. This invention provides a method for suspension polymerization of vinyl chloride, which is characterized in that polymerization is carried out by charging an initiator.
【０００８】本発明について更に詳細に説明する。The present invention will be explained in more detail.
【０００９】本発明に使用される脱イオン水の全量は、
塩化ビニル１００重量部に対して、９０−２００重量部
が好ましい。The total amount of deionized water used in the present invention is:
It is preferably 90-200 parts by weight per 100 parts by weight of vinyl chloride.
【００１０】本発明に使用される懸濁剤は従来知られて
いるもののいずれでもよく、これにはスチレン・マレイ
ン酸コポリマー、部分ケン化ポリビニルアルコール、メ
チルセルロース、ヒドロキシプロピルメチルセルロース
、エチルセルロース、ゼラチン、炭酸カルシウム、リン
酸カルシウム等のうちから１種又は２種以上の組み合わ
せで使用される。The suspending agent used in the present invention may be any of those conventionally known, including styrene-maleic acid copolymer, partially saponified polyvinyl alcohol, methyl cellulose, hydroxypropyl methyl cellulose, ethyl cellulose, gelatin, calcium carbonate, etc. , calcium phosphate, etc., or a combination of two or more thereof.
【００１１】懸濁剤は塩化ビニル１００重量部に対して
０．００１〜５重量部が使用される。 本発明で使用
される重合禁止剤は、通常塩化ビニルの重合反応を禁止
する効果のある重合禁止剤で良く、フェノール系、ホス
ファイト系、チオエーテル系、チアゾール系等の重合禁
止剤が用いられる。The suspending agent is used in an amount of 0.001 to 5 parts by weight per 100 parts by weight of vinyl chloride. The polymerization inhibitor used in the present invention may be a polymerization inhibitor that has the effect of inhibiting the polymerization reaction of vinyl chloride, and phenol-based, phosphite-based, thioether-based, thiazole-based polymerization inhibitors, etc. are used.
【００１２】フェノール系の重合禁止剤としてはハイド
ロキノン、ブチル化ヒドロキシトルエン、ハイドロキノ
ンモノメチルエーテル、３，９−ビス〔１，１−ジメチ
ル−２−｛β−（３−ｔ−ブチル−４−ハイドロキシ−
５−メチルフェニル）プロピオニルオキシ｝エチル〕−
２，４，８，１０−テトラオキサスピロ〔５．５〕ウン
デカン、４，４′−ブチリデンビス−（６−ｔ−ブチル
−３−メチルフェノール、ジブチルヒドロキシトルエン
、オクタデシル−３−（３，５−ジターシャリブチル−
４−ヒドロキシフェノール）−プロピオネート、ペンタ
エリスリチル−テトラキス〔３−（３，５−ジ−ｔ−ブ
チル−４−ヒドロキシフェノール）プロピオネート〕ｎ
−オクタデシル−β−（４′−ヒドロキシ−３′，５′
−ジ−ｔ−ブチルフェール）プロピオネート、ｎ−オク
タデシル−β−（４′−ヒドロキシ−３５′−ジ−ｔ−
ブチルフェニル）プロピオネート、ジラウリルチオジプ
ロピオネート等が挙げられる。Examples of phenolic polymerization inhibitors include hydroquinone, butylated hydroxytoluene, hydroquinone monomethyl ether, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-
5-methylphenyl)propionyloxy}ethyl]-
2,4,8,10-tetraoxaspiro[5.5]undecane, 4,4'-butylidenebis-(6-t-butyl-3-methylphenol, dibutylhydroxytoluene, octadecyl-3-(3,5- Ditertiary butyl
4-hydroxyphenol)-propionate, pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenol)propionate] n
-octadecyl-β-(4'-hydroxy-3',5'
-di-t-butylfer) propionate, n-octadecyl-β-(4'-hydroxy-35'-di-t-
butylphenyl) propionate, dilaurylthiodipropionate, and the like.
【００１３】ホスファイト系の重合禁止剤としては、ト
リフェニルホスファイト、ジフェニルデシルホスファイ
ト、トリオクチルホスファイト、４，４´−ブチリデン
−ビス（３−メチル−６−ｔ−ブチルフェニル−ジ−ト
リデシル）フォスファイト等が挙げられる。Phosphite-based polymerization inhibitors include triphenyl phosphite, diphenyldecyl phosphite, trioctyl phosphite, 4,4'-butylidene-bis(3-methyl-6-t-butylphenyl-di- (tridecyl) phosphite, etc.
【００１４】チオエーテル系の重合禁止剤として２，４
−ビス〔（オクチルチオ）メチル〕−ｏ−クレゾール等
が挙げられる。As a thioether polymerization inhibitor, 2,4
-bis[(octylthio)methyl]-o-cresol and the like.
【００１５】チアゾール系の重合禁止剤とては２−メル
カプトベンゾチアゾール、ジベンゾチアジスルフィド等
が挙げられる。Examples of thiazole-based polymerization inhibitors include 2-mercaptobenzothiazole and dibenzothiadisulfide.
【００１６】これらの重合禁止剤は１種類又は２種類以
上の使用が可能であるが、その使用量としては合計した
量が塩化ビニル１００重量部に対して０．００５−０．
０５重量部が好ましい。添加量が０．００５重量部未満
ではその効果があまりなく、０．０５重量部を越えると
重合反応が遅延して好ましくない。One type or two or more types of these polymerization inhibitors can be used, and the total amount used is 0.005 to 0.00% per 100 parts by weight of vinyl chloride.
05 parts by weight is preferred. If the amount added is less than 0.005 parts by weight, the effect will not be so great, and if it exceeds 0.05 parts by weight, the polymerization reaction will be delayed, which is not preferable.
【００１７】その他添加剤として、通常の塩化ビニルの
懸濁重合で使用されるもの、例えば重合度調整剤、加工
性改良剤、帯電防止剤、ｐＨ調整剤、酸化防止剤、スケ
ール防止剤等の１種類又は２種類以上を使用できる。Other additives include those used in ordinary suspension polymerization of vinyl chloride, such as polymerization degree regulators, processability improvers, antistatic agents, pH regulators, antioxidants, and scale inhibitors. One type or two or more types can be used.
【００１８】添加剤の添加時期は、重合工程のいずれで
も良いが、通常は懸濁剤の仕込みと同じくして仕込まれ
る。The additive may be added at any time during the polymerization process, but it is usually added at the same time as the suspending agent.
【００１９】懸濁剤と重合禁止剤と水との混合は、常温
で十分混合することによって安定な分散状態を得ること
が出来る。A stable dispersion state can be obtained by mixing the suspending agent, polymerization inhibitor, and water sufficiently at room temperature.
【００２０】更に具体的には使用する懸濁剤の曇点又は
熱ゲル化温度以下で上記の混合を行うことが好ましく、
この温度を越えると粗い粒子の生成が多くなる。More specifically, it is preferable to carry out the above mixing at a temperature below the clouding point or thermal gelation temperature of the suspending agent used,
Exceeding this temperature increases the formation of coarse particles.
【００２１】上記の様に常温の脱イオン水の２０〜５０
重量％に懸濁剤、重合禁止剤を仕込み後、通常オートク
レーブ内は脱気処理に付され、オートクレーブ内に存在
する空気を除去する。攪拌を開始した後、好ましくは、
攪拌が定常状態になった後、塩化ビニルと重合系に存在
させる全水量の５０〜８０重量％の重合温度以上に加温
された脱イオン水とを仕込むことによって重合系内を所
定の反応温度まで昇温させ、続いて重合開始剤を仕込ん
でただちに重合する。20 to 50% of deionized water at room temperature as described above.
After the suspending agent and polymerization inhibitor are added to the autoclave, the interior of the autoclave is usually subjected to degassing treatment to remove air present in the autoclave. After starting the stirring, preferably
After the stirring reaches a steady state, the inside of the polymerization system is brought to a predetermined reaction temperature by charging vinyl chloride and deionized water heated to a polymerization temperature of 50 to 80% by weight of the total amount of water present in the polymerization system. Then, a polymerization initiator is charged and polymerization occurs immediately.
【００２２】本発明に使用される塩化ビニルとしては、
塩化ビニル又は塩化ビニルを主成分とするこれと共重合
可能なモノマーとの混合物が使用可能である。塩化ビニ
ルと共重合可能な成分としては例えばエチレン、酢酸ビ
ニル、アクリル酸メチル、アクリロニトリル、塩化ビニ
リデン等が上げられる。[0022] As the vinyl chloride used in the present invention,
It is possible to use vinyl chloride or mixtures based on vinyl chloride with monomers copolymerizable therewith. Examples of components copolymerizable with vinyl chloride include ethylene, vinyl acetate, methyl acrylate, acrylonitrile, and vinylidene chloride.
【００２３】本発明で使用される重合開始剤はアゾビス
−α，α′−ジメチルバレロニトリル、２，２′−アゾ
ビス−２，４−ジメチル−４−メトキシバレロニトリル
等のアゾ化合物、ジイソプロピルパーオキシジカーボネ
ート、ジ−２−エチルヘキシルパーオキシジカーボネー
ト、ジ−（β−エトキシエチル）パーオキシジカーボネ
ート、ｔ−ブチルパーオキシジカーボネート、アセチル
シクロヘキシルスルホニルパーオキサイド、ｔ−ブチル
パーオキシピバレート、ｔ−ブチルパーオキシネオデカ
ネート、ラウロイルパーオキサイド等の有機過酸化物が
あげられる。The polymerization initiator used in the present invention is an azo compound such as azobis-α,α'-dimethylvaleronitrile, 2,2'-azobis-2,4-dimethyl-4-methoxyvaleronitrile, diisopropylperoxy Dicarbonate, di-2-ethylhexyl peroxydicarbonate, di-(β-ethoxyethyl)peroxydicarbonate, t-butylperoxydicarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxypivalate, t- Examples include organic peroxides such as butyl peroxyneodecanate and lauroyl peroxide.
【００２４】重合開始剤は塩化ビニル１００重量部に対
して０．０００１〜５重量部が使用される。The polymerization initiator is used in an amount of 0.0001 to 5 parts by weight per 100 parts by weight of vinyl chloride.
【００２５】これらの重合開始剤は、希釈剤と共に使用
することもできる。希釈剤としては、メタノール、エタ
ノール等の低級アルコール、トルエン、キシレン等の芳
香族炭化水素、炭素数１２以上の常温で液体の脂肪族炭
化水素、アセトン等が挙げられる。These polymerization initiators can also be used together with a diluent. Examples of the diluent include lower alcohols such as methanol and ethanol, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons having 12 or more carbon atoms that are liquid at room temperature, and acetone.
【００２６】希釈率としては、５〜５０重量％に希釈す
るのが好ましい。なぜなら重合開始剤を均一分散させ、
粒度の安定性およびフィシュアイの削減を図ることがで
きるからである。５重量％未満では希釈剤が多くなって
、経済的でなく、又５０重量％越えると希釈剤を使用す
る効果が十分発現されない場合がある。The dilution rate is preferably 5 to 50% by weight. This is because the polymerization initiator is uniformly dispersed,
This is because particle size stability and fisheye reduction can be achieved. If it is less than 5% by weight, the amount of diluent increases and it is not economical, and if it exceeds 50% by weight, the effect of using the diluent may not be fully realized.
【００２７】本発明の方法は通常の塩化ビニルの懸濁重
合が行われる温度範囲で実施する事ができる。従って使
用する加温された脱イオン水の温度としては、重合温度
〜１００℃の水、好ましくは６０〜９０℃であるが、こ
れは重合温度、温水の仕込量、ジャケットからの加熱能
力及び重合処方等に応じて適宜決めることが可能である
。The process of the present invention can be carried out in the temperature range in which conventional suspension polymerization of vinyl chloride is carried out. Therefore, the temperature of the heated deionized water to be used is water at a temperature between the polymerization temperature and 100°C, preferably 60 to 90°C, but this depends on the polymerization temperature, the amount of hot water charged, the heating capacity from the jacket, and the polymerization temperature. It can be determined as appropriate depending on the prescription, etc.
【００２８】[0028]
【実施例】以下実施例により本発明を説明するが、本発
明は、これらによって制限されるものではない。
評価
実施例における粉体特性等の評価は次の様にして行った
１．粒度分布 ＪＩＳ標準のふるいを用いて測定した
。
２．フィシュアイ
Ａ配合
レジン １００重量部
ＤＯＰ ５０
〃Ｃａ−Ｚｎ 系安定剤 ２
〃群青
３ 〃Ｂ評価
上記の配合で１５０℃のミキシングロールで３分間混練
し、０．３５ｍｍのシートを作成した。このシートを使
用し５０ｃｍ２ 中にフィシュアイが何個あるかを数え
た。
３．スケール付着状況
○ 良好
× 悪い
４．ガラス状粒子の生成
○ 生成しない
× 生成する。EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. Evaluation of powder properties, etc. in evaluation examples was performed as follows.1. Particle size distribution Measured using a JIS standard sieve. 2. Fisheye A blended resin 100 parts by weight DOP 50
〃Ca-Zn stabilizer 2
〃Gunjo
3 B Evaluation The above formulation was kneaded for 3 minutes using a mixing roll at 150°C to create a 0.35 mm sheet. Using this sheet, we counted the number of fisheyes in 50 cm2. 3. Scale adhesion status ○ Good × Bad 4. Formation of glassy particles ○ Not formed × Formed.
【００２９】実施例１
１ｍ３ オートクレーブ中に常温の塩化ビニル１００重
量部に対して、脱イオン水５５重量部、部分ケン化ポリ
ビニルアルコール０．０６重量部、ジブチルヒドロキシ
トルエン０．０２重量部を仕込み、オートクレーブ内を
脱気した。Example 1 In a 1 m3 autoclave, 55 parts by weight of deionized water, 0.06 parts by weight of partially saponified polyvinyl alcohol, and 0.02 parts by weight of dibutylhydroxytoluene were charged to 100 parts by weight of vinyl chloride at room temperature. The inside of the autoclave was evacuated.
【００３０】攪拌を開始後、３０℃の塩化ビニル１００
重量部を仕込み、ついで８０℃に加温した脱イオン水７
５重量部を仕込み、オートクレーブ内の温度を５７℃に
してからジ−２−エチルヘキシルパーオキシジカーボネ
ート０．０２重量部を仕込んで重合を開始した。オート
クレーブ内の圧力が５７℃における塩化ビニルの飽和蒸
気圧により、２．０Ｋｇ／ｃｍ２ 低下したところで重
合を停止し、未反応塩化ビニルを回収して、撹拌を停止
した。得られたスラリーを脱水乾燥し、塩化ビニルポリ
マーを得た。得られたポリマーの粒度分布及びフィシュ
アイ試験の結果を表１に示す。After starting stirring, 100% vinyl chloride at 30°C
7 parts by weight of deionized water, which was then heated to 80°C.
After charging 5 parts by weight and raising the temperature inside the autoclave to 57° C., 0.02 parts by weight of di-2-ethylhexyl peroxydicarbonate was charged to start polymerization. Polymerization was stopped when the pressure inside the autoclave decreased by 2.0 kg/cm2 due to the saturated vapor pressure of vinyl chloride at 57°C, unreacted vinyl chloride was recovered, and stirring was stopped. The obtained slurry was dehydrated and dried to obtain a vinyl chloride polymer. Table 1 shows the particle size distribution of the obtained polymer and the results of the fisheye test.
【００３１】実施例２
実施例１において、ジ−２−エチルヘキシルパーオキシ
ジカーボネート０．０２重量部をメタノールで３０重量
％溶液に変更した以外はまったく同様に実施した。得ら
れたポリマーの試験結果を表１に示す。Example 2 The same procedure as in Example 1 was carried out except that 0.02 parts by weight of di-2-ethylhexyl peroxydicarbonate was changed to a 30% by weight solution with methanol. Table 1 shows the test results of the obtained polymer.
【００３２】実施例３
実施例１において、３０℃の塩化ビニル１００重量部と
８０℃に加温した脱イオン水７５重量部とを同時に仕込
んで、オートクレーブ内の温度を５７℃にしてからジ−
２−エチルヘキシルパーオキシジカーボネート０．０２
重量部を仕込んで重合を開始した以外まったく同様に実
施した。得られたポリマーの試験結果を表１に示す。Example 3 In Example 1, 100 parts by weight of vinyl chloride at 30°C and 75 parts by weight of deionized water heated to 80°C were charged at the same time, and the temperature inside the autoclave was raised to 57°C.
2-Ethylhexyl peroxydicarbonate 0.02
The procedure was carried out in exactly the same manner except that the polymerization was started by adding the same amount by weight. Table 1 shows the test results of the obtained polymer.
【００３３】実施例４
実施例１において、反応温度（オートクレーブ内の温度
）を６４℃にし、脱イオン水の添加量を常温の脱イオン
水３５重量部、８０℃に加温した脱イオン水を９５重量
部に変更した以外まったく同様に実施した。得られたポ
リマーの試験結果を表１に示す。Example 4 In Example 1, the reaction temperature (temperature inside the autoclave) was set to 64°C, and the amount of deionized water added was 35 parts by weight of deionized water at room temperature and deionized water heated to 80°C. The same procedure was carried out except that the amount was changed to 95 parts by weight. Table 1 shows the test results of the obtained polymer.
【００３４】比較例１
１ｍ３ オートクレーブ中に部分ケン化ポリビニルアル
コール０．０６重量、ジブチルヒドロキシトルエン０．
０２重量部を含む３０℃の脱イオン水１３０重量部を仕
込み、脱気した。攪拌を開始し、３０℃の塩化ビニル１
００重量部を仕込んだ後に、ジャケットを８０℃の温水
で加熱し、オートクレーブ内の温度を５７℃にしてから
ジ−２−エチルヘキシルパーオキシジカーボネート０．
０２重量部を仕込んで重合を開始した。この後、実施例
１と同じ条件下で処理して塩化ビニルポリマーを得た。
得られたポリマーの試験結果を表１に示す。Comparative Example 1 0.06 weight of partially saponified polyvinyl alcohol and 0.06 weight of dibutylhydroxytoluene were placed in a 1 m3 autoclave.
130 parts by weight of deionized water at 30°C containing 0.2 parts by weight was charged and degassed. Start stirring and add vinyl chloride 1 at 30°C.
After charging 0.00 parts by weight of di-2-ethylhexyl peroxydicarbonate, the jacket was heated with 80°C hot water to bring the temperature inside the autoclave to 57°C.
02 parts by weight was added to start polymerization. Thereafter, it was treated under the same conditions as in Example 1 to obtain a vinyl chloride polymer. Table 1 shows the test results of the obtained polymer.
【００３５】比較例２
１ｍ３ オートクレーブ中に脱イオン水５５重量部、部
分ケン化ポリビニルアルコール０．０６重量部を仕込み
、オートクレーブ内を脱気した。３０℃の塩化ビニル１
００重量部とジ−２−エチルヘキシルパーオキシジカー
ボネート０．０２重量部とを仕込んだ後、攪拌を開始し
、続いて８０℃に加温した脱イオン水７５重量部を仕込
んでオートクレーブ内の温度を５７℃にして重合を開始
した。この後、実施例１と同じ条件下で処理して塩化ビ
ニルポリマーを得た。得られたポリマーの試験結果を表
１に示す。Comparative Example 2 A 1 m3 autoclave was charged with 55 parts by weight of deionized water and 0.06 parts by weight of partially saponified polyvinyl alcohol, and the inside of the autoclave was degassed. Vinyl chloride 1 at 30℃
After charging 0.00 parts by weight and 0.02 parts by weight of di-2-ethylhexyl peroxydicarbonate, stirring was started, and then 75 parts by weight of deionized water heated to 80°C was charged to adjust the temperature inside the autoclave. The temperature was raised to 57°C to initiate polymerization. Thereafter, it was treated under the same conditions as in Example 1 to obtain a vinyl chloride polymer. Table 1 shows the test results of the obtained polymer.
【００３６】比較例３
比較例１において、オートクレーブ内の温度を６４℃に
した以外まったく同様に実施した。得られたポリマーの
試験結果を表１に示す。Comparative Example 3 The same procedure as in Comparative Example 1 was carried out except that the temperature inside the autoclave was changed to 64°C. Table 1 shows the test results of the obtained polymer.
【００３７】比較例４
特開昭５７−５７０４に記載の方法に従い、１ｍ３ オ
−トクレ−ブ中に８０℃に加温した脱イオン水１３０重
量部、部分ケン化ポリビニルアルコ−ル０．００６重量
部、ジ−２−エチルヘキシルパ−オキシジカ−ポネ−ト
０．００２重量部と３０℃の塩化ビニル１００重量部を
撹拌しながら同時に仕込んでオ−トクレ−ブ内の温度を
５７℃にして重合を開始した。この後、実施例１と同じ
条件下で処理して塩化ビニルポリマ−を得た。得られた
ポリマ−の試験結果を表１に示す。Comparative Example 4 130 parts by weight of deionized water heated to 80°C and 0.006 parts by weight of partially saponified polyvinyl alcohol were placed in a 1 m3 autoclave according to the method described in JP-A-57-5704. 0.002 parts by weight of di-2-ethylhexyl peroxydicarbonate and 100 parts by weight of vinyl chloride at 30°C were charged simultaneously with stirring, and the temperature inside the autoclave was raised to 57°C for polymerization. started. Thereafter, it was treated under the same conditions as in Example 1 to obtain a vinyl chloride polymer. Table 1 shows the test results of the obtained polymer.
【００３８】比較例５
特開昭６０−４７００７に記載の方法に従い、１ｍ３
オ−トクレ−ブ中に脱イオン水３０重量部、３０℃塩化
ビニル１０重量部、部分ケン化ポリビニルアルコ−ル０
．０６重量部、ジ−２−エチルヘキシルパ−オキシジカ
−ボネ−ト０．００２重量部を３０℃以下の温度で均一
混合し、ついで撹拌しながら８０℃に加温した脱イオン
水を１００重量部になる様に仕込んでオ−トクレ−ブ内
の温度を５７℃にして重合を開始した。この後、実施例
１と同じ条件下で処理して塩化ビニルポリマ−を得た。
得られたポリマ−の試験結果を表１に示す。Comparative Example 5 According to the method described in JP-A-60-47007, 1 m3
In an autoclave, 30 parts by weight of deionized water, 10 parts by weight of vinyl chloride at 30°C, 0 parts by weight of partially saponified polyvinyl alcohol.
．． 0.06 parts by weight of di-2-ethylhexyl peroxydicarbonate and 0.002 parts by weight of di-2-ethylhexyl peroxydicarbonate were uniformly mixed at a temperature below 30°C, and then 100 parts by weight of deionized water heated to 80°C with stirring was added. The temperature inside the autoclave was raised to 57°C to start polymerization. Thereafter, it was treated under the same conditions as in Example 1 to obtain a vinyl chloride polymer. Table 1 shows the test results of the obtained polymer.
【００３９】比較例６
特開昭５４−４７７８５に記載の方法に従い、１ｍ３
オ−トクレ−ブ中に３０℃以下の水３０重量部、部分ケ
ン化ポリビニルアルコ−ル０．０６重量部、ジ−２−エ
チルヘキシルパ−オキシジカ−ボネ−ト０．０２重量部
を仕込み、撹拌混合した後、８０℃に加温した脱イオン
水１００重量部を仕込んでオ−トクレ−ブ内の温度を５
７℃にして重合を開始した。この後、実施例１と同じ条
件下で処理して塩化ビニルポリマ−を得た。得られたポ
リマ−の試験結果を表１に示す。Comparative Example 6 According to the method described in JP-A-54-47785, 1 m3
30 parts by weight of water below 30°C, 0.06 parts by weight of partially saponified polyvinyl alcohol, and 0.02 parts by weight of di-2-ethylhexyl peroxydicarbonate were placed in an autoclave and stirred. After mixing, 100 parts by weight of deionized water heated to 80°C was charged, and the temperature inside the autoclave was raised to 5°C.
Polymerization was started at 7°C. Thereafter, it was treated under the same conditions as in Example 1 to obtain a vinyl chloride polymer. Table 1 shows the test results of the obtained polymer.
【００４０】[0040]
【表１】[Table 1]
【００４１】[0041]
【発明の効果】以上の説明から明らかなように、本発明
の方法によれば塩化ビニルの重合における昇温時間を著
しく短縮することが可能となり、併せてフィシュアイそ
の他の物性を損なうことなく生産性の向上を計ることが
可能である。Effects of the Invention As is clear from the above explanation, according to the method of the present invention, it is possible to significantly shorten the heating time in the polymerization of vinyl chloride, and at the same time, it is possible to produce fisheye and other physical properties without damaging them. It is possible to measure the improvement of sexual performance.
Claims (1)
クレーブ中に重合系の全水量のうち、２０〜５０重量％
の常温の脱イオン水、懸濁剤、重合禁止剤を仕込み、攪
拌を開始した後、塩化ビニルと重合系の全水量の５０〜
８０重量％の重合温度以上に加温された脱イオン水とを
仕込むことによって重合系内を反応温度まで昇温させ、
続いて重合開始剤を仕込んで重合を行うことを特徴とす
る塩化ビニルの懸濁重合法。Claim 1: In the suspension polymerization method of vinyl chloride, 20 to 50% by weight of the total amount of water in the polymerization system is added to the autoclave.
After adding deionized water at room temperature, a suspending agent, and a polymerization inhibitor and starting stirring, 50 to 50% of the total amount of water in the vinyl chloride and polymerization system was added.
The temperature inside the polymerization system is raised to the reaction temperature by charging deionized water heated to 80% by weight or above the polymerization temperature,
A suspension polymerization method for vinyl chloride, which is characterized in that a polymerization initiator is subsequently charged and polymerization is carried out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2370091A JP2912955B2 (en) | 1991-01-25 | 1991-01-25 | Suspension polymerization of vinyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2370091A JP2912955B2 (en) | 1991-01-25 | 1991-01-25 | Suspension polymerization of vinyl chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04248811A true JPH04248811A (en) | 1992-09-04 |
| JP2912955B2 JP2912955B2 (en) | 1999-06-28 |
Family
ID=12117664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2370091A Expired - Lifetime JP2912955B2 (en) | 1991-01-25 | 1991-01-25 | Suspension polymerization of vinyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2912955B2 (en) |
-
1991
- 1991-01-25 JP JP2370091A patent/JP2912955B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2912955B2 (en) | 1999-06-28 |
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